Method for reacting organic halides

ABSTRACT

A method for carrying out reactions of the Friedel-Crafts type, such as alkylation, acylation, polymerization, sulfonylation and dehydrohalogenation. The reactions are catalyzed by arene-metal tricarbonyl complexes and when the reaction vessel contains aromatic substrates the catalyst may be generated in situ from a metallic hexacarbonyl. The arene-metal tricarbonyl catalyst is more selective than conventionally employed Friedel-Craft catalysts in that it yields generally para isomers with little of the ortho variety and very little if any of the meta variety when the aromatic substrate is reacted with organic halide. It is also possible to form the arene-metal tricarbonyl catalyst outside of the reaction vessel and then proceed by adding it to the vessel containing the substrate and the organic halide as is the case with dehydrohalogenation reactions wherein there are no aromatic rings available, the substrate in that instance being aliphatic.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. Ser. No. 339,637,filed Mar. 9, 1973 now U.S. Pat. No. 3,832,403, which is in turn acontinuation-in-part application of U.S. Ser. No. 119,908, filed Mar. 1,1971 now abandoned.

BACKGROUND OF THE INVENTION

Substitution of halogens from organic compounds by other organic groupsor the mere removal of halogens, without substitution, to form neworganic compounds is well known by a variety of standard name reactions.The Friedel-Crafts type of reactions, usually carried out by thecatalyst aluminum trichloride, are an example.

The reactivity of the arene-metal tricarbonyl complexes has also beenexamined and it is known that the tricarbonylchlorobenzenechromiumcomplex will enter into a nucleophilic reaction with methyl alcohol toform the anisole complex. Further, electrophilic reactions are alsofacilitated such as Friedel-Crafts acetylation of thetricarbonyl-benzene chromium complex with acetyl chloride in thepresence of aluminum trichloride. Both types of reaction yield a productwhich retains the arene-metal tricarbonyl complex.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a methodfor reacting organic halides in alkylations, acylations,polymerizations, sulfonylations and dehydrohalogenations.

It is another object of the present invention to provide a method forcarrying out these reactions in the presence of an arene-metaltricarbonyl catalyst.

It is a further object of the present invention to employ a catalystwhich is easier to use, with respect to storage and handling, in thatthe catalyst may be generated in solution within the reaction vessel orwithout the reaction vessel and subsequently added thereto.

It is yet another object of the present invention to employ a catalystwhich promotes attack on the aromatic ring generally at the paraposition rather than at the ortho position and usually excludes attackat the meta position.

These and other objects of the invention, and the advantages thereof,will be apparent in view of the detailed disclosure of the invention asset forth below.

In general, it has now been found that an organic halide RX, and anarene-metal tricarbonyl represented by the general formula, ##SPC1##

Will react to form a carbonium ion R⁺.

It was further found that the highly reactive carbonium ion will releasea hydrogen ion, or react in situ and in a repetitive process with theoriginal organic halide or with other organic compounds present withinthe reaction vessel. Many different classes of products may Be formed bypredetermined selection of the appropriate organic reactants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The catalyst may be prepared in advance of a catalysis reactionaccording to the reaction mechanism ##SPC2##

where R' is selected from the class consisting of electron donating andring activating groups such as hydrogen, alkyl groups having from 1 toabout 6 carbon atoms, alkoxide groups having from 1 to about 4 carbonatoms, aryl and aryloxide groups having from 6 to about 12 carbon atomsincluding alkyl substituents, amino and hydroxide. The metal, M, isselected from the group consisting of Cr, Mo, and W with molybdenumbeing preferred.

Representative alkyl groups include methyl, ethyl, isopropyl, t-butyl,pentyl, hexamethyl and the like. Representative alkoxide groups includemethoxy, ethoxy, propoxy, butoxy, sec-butoxy and the like.

Representative aryl groups include phenyl, napthyl and the phenyl ringwith substituted alkyl groups such as methyl, ethyl, propyl, butyl,sec-butyl, pentyl, 2-pentyl, hexamethyl and the like. A representativearyloxide is diphenyl ether.

R' may further be selected from the class consisting of ringdeactivating and electron withdrawing groups such as the halides, thehaloalkyls, the alkylbenzoate esters, the aldehydes and sulfonylhalides, particularly sulfonyl chloride. Representative halides arefluoro, chloro and bromo, and representative alkylbenzoate esters arethose having from 1 to 3 carbon atoms such as methyl benzoate, ethylbenzoate, propyl benzoate and isopropyl benzoate. Representativealdehydes are those having from 1 to 4 carbon atoms. Representativehaloalkyl groups include methyl bromide, methyl chloride and methylfluoride.

In addition to the aforementioned mono-substituted phenyl compoundswhich may be utilized it is also possible to select poly-substitutedphenyl compounds having up to five substituent groups. The genericformula for such a compound may be expressed as follows: ##SPC3##

wherein R' may be the same as any of the aforementioned R' groupsincluding hydrogen. As will be obvious to one skilled in the art, alarge number of the existing poly-substituted phenyl compounds can thusbe used in accordance with the teaching of this pioneer invention. Sinceit would be impractical to provide an all inclusive listing, only someof the representative compounds according to formula F(3) will be setforth.

Representative compounds wherein one or more of the R' groups are otherthan hydrogen include anisole, chlorobenzene, benzyl chloride, benzylfluoride, phenol, toluene, t-butyl benzene, o,m and p-dichlorobenzene,diphenyl ether, biphenyl, o,m and p-xylene, p-toluene sulfonyl chloride,methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate,2,3-dimethoxyaniline, 2,4-dihydroxytoluene, 3,4-dimethoxytoluene,4-hydroxy-3-methoxytoluene, 1,2,4,5-tetramethylbenzene,3,4,5-trihydroxytoluene and 1,3-dihydroxy-4,5,6-trimethylbenzene.

Selection of any specific aromatic compound will of course be dependentupon factors such as the product desired and the availability orexistence of the compound. A person skilled in the art will generallyknow numerous existing compounds. Moreover, as to other compounds, anystandard reference book, such as the CRC Handbook of Chemistry andPhysics, could be consulted thus enabling the skilled artisan to obtainreadily the names of other existing compounds.

Preparation of the catalyst according to F(2) is necessarily precedentto a catalysis reaction when aryl radicals are neither present norconstituents of the reactants chosen to form the product compounds.Thus, in the case of dehydrohalogenation reactions, the catalyst willpromote the formation of the olefin, but it must be prepared in advanceas there are no aromatic rings available in the reaction vessel.

Thus, a utility of the present invention is that this catalyst may begenerated during the catalysis reaction. Thus, when the metalhexacarbonyl and a substrate reactant having an aryl radical constituentare brought together in a reaction vessel, the arene-metal tricarbonylcatalyst will be generated in situ. Upon the addition of the desiredorganic halide, the particlar reaction, e.g., alkylation, acylation,polymerization, sulfonylation, will then proceed to form the desiredproducts.

According to the method of the present invention, aromatic substratesare combined with organic halides, having the generic formula RX, in thereaction vessel. The catalyst removes the halogen forming a highlyreactive carbonium ion on the organic moiety R. Subsequent attack by thecarbonium ion upon the substrate molecule yields a product, resultingfrom the attachment of the organic radical R to the substrate, and ahydrogen ion. The hydrogen ion quickly removes the halogen with at leastpartial regeneration of the catalyst. In this manner alkylations,acylations, polymerizations and sulfonylations occur. Of course, thecatalyst also promotes dehydrohalogenation. However, since there is noaromatic substrate the catalyst merely removes the halogen from theorganic halide to yield an olefin.

The organic halide RX, wherein X is generally selected from bromine,chlorine and fluorine, will be chosen according to the desired reaction,e.g., alkyl aryl or acyl halides for alkylation and acylation, sulfonylhalides for sulfonylation and polymerization and alkyl halides fordehydrohalogenation. The organo group, or R, may therefore be selectedfrom the class consisting of alkyl radicals having from 1 to about 20carbon atoms, aryl radicals having from 7 to about 12 carbon atoms,alkoxide radicals having from 1 to about 4 carbon atoms and aldehydeshaving from 1 to about 4 carbon atoms, and haloalkyl groups such asmethyl bromide, methyl chloride and methyl fluoride. When aryl radicalsare utilized having alkyl substituents for the alkylation andpolymerization reactions it is necessary for the halogen to be bonded tothe substituent rather than the ring inasmuch as the catalyst removes,for instance, chlorine much more readily from benzyl chloride than fromchlorobenzene.

Representative alkyl groups include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl isomers thereof and the like.Representative aryl radicals include tolyl, xylyl, methyl naphthyl andthe like. Furthermore, when selecting the xylenes, dihalo compounds maybe utilized as the catalyst can readily remove both halogens from theirmethyl partner. As before, the skilled artisan can refer to a referencehandbook to ascertain the existing organic halides which he may desireto react.

Whether the catalyst is prepared within the reaction vessel by reactingmolybdenum hexacarbonyl with the aromatic substrate, or it is separatelyprepared and added, the reactants are all placed within the reactionvessel. Generally, the reactants are soluble within the substrate;however, if such is not the case, the reaction may be carried out inheptane or any other saturated liquid hydrocarbon or any aryl such asbenzene or substituted benzene. The reaction is preferably carried outin an inert atmosphere such as nitrogen. In order to generally initiatethe reaction, the vessel is usually fitted with a reflux condenser andheated from ambient temperatures through a temperature range of a fewdegrees to approximately 135°C, depending upon the type of reaction andthe reactants. Reaction time is also dependent upon the latter factorsand accordingly ranges from about 1 hour to about 36 hours or longer.During this time it is necessary to keep the reactants mixed which maybe readily accomplished with a conventional magnetic stirrer or thelike. Mechanisms for the various reactions are as follows:

An alkylation according to the present invention is thought to proceedaccording to the following reaction mechanism; ##SPC4##

where R is an alkyl or aryl group as noted above

and R' is hydrogen, alkyl, alkoxide, sulfonyl chloride, hydroxide, arylor aryl oxide as noted above

and M is a metal from the group, Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

The catalyst is formed in the reaction vessel from part of the aromaticsubstrate reactant or it may be added in its active form whereby Step 1is omitted. In Step 2, it proceeds to remove the halogen from theorganic halide, RX, resulting in the formation of a highly reactivecarbonium ion, R⁺, which subsequently attacks the remaining part of thearomatic substrate, as in Step 3, with concurrent release of a hydrogenion. In Step 4, the hydrogen ion removes the halogen and the catalyst isregenerated.

An acylation according to the present invention is thought to proceedaccording to the following reaction mechanism; ##SPC5## where R is analkyl or aryl group as noted above

and R' is hydrogen, alkyl, alkoxide or hydroxide, aryl or aryloxide asnoted above

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

The catalyst is again formed in Step 1, as described before or merelyadded directly to the reactants. In Step 2 it proceeds to remove thehalogen from the organic acid halide resulting in the formation of ahighly reactive acyl cation RC^(+=O), which subsequently attacks thearomatic substrate reactant, as in Step 3, with concurrent release of ahydrogen ion. In Step 4, the hydrogen ion removes the halogen and thecatalyst is regenerated.

Two types of polymers may be produced according to the presentinvention. A branched structure may be formed by the polymerization ofone monomeric substance or the combination of two monomers. A linearpolymer may be produced by selecting an aryl substrate, A, having onlytwo positions subject to carbonium ion attack and having ligands at eachof the other positions relatively unsusceptible to carbonium ion attack.The organic halide selected, B, is a dihalo-compound such that carboniumions may form at two ends of the molecule, thus forming a linearpolymerization of the type AB.

Polymerization to form a branched polymer according to the presentinvention is thought to proceed according to the following reactionmechanism; ##EQU1## where R is an aryl radical as noted above

and R' is alkyl, alkoxide, or haloalkyl as noted above,

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

The organic halide has an aryl ring, and therefore will react withmolybdenum hexacarbonyl as in Step 1, or if desired, the active form ofthe catalyst may be prepared separately and added to the monomerichalide R--R'-X as in Step 2 where the halogen is removed resulting inthe formation of a highly reactive carbonium ion, R--R'⁺, whichsubsequently attacks the organic halide as in Step 3, with concurrentrelease of a hydrogen ion. The catalyst is again regenerated as by Step4.

The reaction generally proceeds with substantial conversion of themonomer to the dimer R--R'--R--R'--X; then loss of the halogen againresults in a carbonium ion which combines in a repetitive process toproduce a polymer having an average number molecular weight ranging fromapproximately 5,000 to 30,000. Owing to the reactive sites of a phenylring, o, m, and p, to the ligand R', the polymer is highly branched.

Polymerization to form a linear copolymer according to the presentinvention is thought to proceed according to the following reactionmechanism: ##SPC6##

where R' is alkyl, alkoxide, aryl, aryloxide or hydroxide as noted above

and R is alkyl, alkoxide, aldehyde, sulfonyl or haloalkyl as notedabove,

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

Removal of both halides from the dihalo-compound produces two reactivecarbonium ions which will combine with the available positions of thearomatic substrate compound in a repetitive process to form a linearcopolymer of average number molecular weight ranging between 5,000 and30,000.

A sulfonylation according to the present invention is thought to proceedaccording to the following reaction mechanism: ##SPC7##

where R is an alkyl or aryl group as noted above

and R' is hydrogen, alkyl, alkoxide, aryl, aryloxide or hydroxide asnoted above

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

The catalyst is again formed in Step 1, as described before or merelyadded directly to the reactants. In Step 2 it proceeds to remove thehalogen from the sulfonyl halide, R--SO₂ --X, resulting in the formationof a highly reactive sulfonium ion, R--S^(+O) ₂, which subsequentlyattacks the aromatic substrate reactant as in Step 3, with concurrentrelease of a hydrogen ion. In Step 4, the hydrogen ion removes thehalogen and the catalyst is regenerated.

A dehydrohalogenation according to the present invention is thought toproceed according to the following reaction mechanism: ##SPC8##

where R is an alkyl group as noted above

and R' is hydrogen, alkyl, alkoxide, sulfonyl chloride, amino, aryl andaryloxide, halide, hydroxide and alkylbenzoate esters as noted above

and M is a metal from the group Cr, Mo and W,

and X is a halogen from the group of Br, Cl and F.

In this reaction it is desirable to form the active catalyst apart fromthe reactants since M(CO)₆ will not combine with an alkyl halide and ifan aryl halide is present some alkylation will occur. In Step 1, thecatalyst removes the halogen from the alkyl halide, R--X, resulting inthe formation of a highly reactive carbonium ion, R⁺. With subsequentloss of a hydrogen ion, as in Step 2, an alkene product is formed. InStep 3, the hydrogen ion removes the halogen and the catalyst isregenerated.

The invention will be more fully understood by reference to thefollowing examples which describe the various types of reactions.

EXAMPLE I

An alkylation by an organic halide of an aryl compound is promoted bythe combination of 12.2 gms. of phenol; 20 cc. of t-butyl chloride; and50 mg. of molybdenum hexacarbonyl in 120 cc. of the solvent heptane.These reactants are placed in a suitable vessel and mixed as by amagnetic stirring apparatus. The vessel is fitted with a refluxcondenser and is then heated, to approximately 98°C. for 18 to 24 hours.At the end of this time period, the desired product is separated bysuitable means well known to one skilled in the art.

EXAMPLE II

An acylation by an acid halide of an aryl compound is promoted by thecombination of 125 cc. of anisole; 4 cc. of acetyl chloride and 25-50mg. of molybdenum hexacarbonyl. These reactants are placed in a suitablevessel, and thoroughly mixed while refluxing at approximately 100°C. for36 hours. At the end of this time period, the desired product isseparated by suitable means.

EXAMPLE III

A polymerization of an organic halide to form a branched polymer ispromoted by the combination of 100 gms. of benzyl chloride with 50 mg.of molybdenum hexacarbonyl. The compounds are placed in a suitablevessel, mixed and refluxed at approximately 100°C. for 1 hour. At theend of this time period, the branched polymer is separated by suitablemeans.

EXAMPLE IV

A linear polymer may be formed by combining 7.3 gms. of a,a'dichloro-p-xylene; 5.4 gms. of durene, and 10 mg. of molybdenumhexacarbonyl in 100 cc. of the solvent, decalin. The reactants areplaced in a suitable vessel, mixed and refluxed at approximately125°-130°C. for 3 hours. At the end of this time period the linearpolymer is separated by suitable means.

EXAMPLE V

A sulfonylation of an aryl sulfonyl halide is promoted by combining 160cc. of toluene; 3.8 gms. of p-tosyl chloride and 25 to 50 mg. ofmolybdenum hexacarbonyl in a suitable vessel. The reactants are thenmixed and refluxed at approximately 110°C. for 36 hours. At the end ofthis time period, the desired product is separated by suitable means.

EXAMPLE VI

A dehydrohalogenation of an organic halide is promoted by thecombination of 100 cc. of t-butyl chloride with 200 mg. of toluenemolybdenum tricarbonyl. The compounds are placed in a suitable vessel,mixed and refluxed at approximately 51°C. for 4 hours. At the end ofthis time period the desired product is separated by suitable means.

The results of these and similar reactions have been set forth in Tables1-5 below. In Table 1, examples 1-10 represent alkylations. In Table 2,examples 1-6 represent acylations. In Table 3, example 1 representsformation of a linear polymer and examples 2-3 represent formation ofbranched polymers and 4-5 represent branched or linear polymers. InTable 4, examples 1-3 represent sulfonylations. In Table 5, example 1, adehydrohalogenation reaction was attempted without the arene metaltricarbonyl catalyst and no reaction was evidenced. In example 2, thecatalyst was present, being first prepared as in F(2) above, and thealkene, isobutylene, was quickly formed thereby. Although the productmay be isolated, by continuing the reaction, the polymeric productswhich are known to occur when isobutyl cations attack isobutylene areprepared.

Thus, it can be seen that the disclosed invention carries out theobjects of the invention set forth above. As will be apparent to thoseskilled in the art, many modifications can be made without departingfrom the spirit of the invention herein disclosed and described, thescope of the invention being limited solely by the scope of the attachedclaims.

                                      Table 1                                     __________________________________________________________________________    Alkylation Reactions                                                          Aromatic    Organic    Added  Reaction                                        Substrate   Halide    Catalyst                                                                             Conditions                                                                          Yield  Comments                            __________________________________________________________________________    1.   Toluene                                                                             t-butyl chloride                                                                         Mo(CO).sub.6                                                                         Reflux                                                                              17.9 g                                                                             Exclusively para                           (100 ml)                                                                            (12.6 g)   (0.20 g)                                                                             5 hr  88%  substitution                          2.   Toluene                                                                             t-butyl chloride                                                                         TolMo(CO).sub.3                                                                      Reflux                                                                              16.7 g                                          (100 ml)                                                                            (12.6 g)   (0.20 g)                                                                             1 hr  81.8% -3.                                                                          Toluene Cyclohexyl Mo(CO).sub.6 Re                                            flux 19.7 g                                (160 ml)                                                                            chloride (10 g)                                                                          (0.05 g)                                                                             6 hr  84.5%                                      4.   Toluene                                                                             Benzyl     Mo(CO).sub.6                                                                         Reflux                                                                              16.4 g                                                                             100% alkylation, 10%                       (200 ml)                                                                            chloride (12.6 g)                                                                        (0.03 g)                                                                             12 hr 90%  polymer, 90% totyl-                                                           phenylmethane                         5.   Toluene                                                                             n-propyl chloride                                                                        TolMo(CO).sub.3                                                                      130°                                                                          7.8 g                                                                             Carried out in glass-                      (50 ml)                                                                             (8.9 g)    (0.20 g)                                                                             6 hr  50.5%                                                                              lined Parr bomb, product                                                      exclusively p-cymene                  6.   t-butyl                                                                             n-chloroheptane                                                                          Mo(CO).sub.6                                                                         140°                                                                              Only secondary                             benzene                                                                             (8.8 g)    (0.01 g)                                                                             24 hr      alkylates obtained                         (55 ml)                                                                  7.   Toluene                                                                             Cyclohexyl TolMo(CO).sub.3                                                                      Reflux                                                                              12.8 g                                          (75 ml)                                                                             fluoride (11.2 g)                                                                        (0.1 g)                                                                              6 hr  67.3%                                      8.   Toluene                                                                             Cyclohexyl TolMo(CO).sub.3                                                                      Reflux                                                                               6.7 g                                                                             Extensive catalyst                         (80 ml)                                                                             bromide (26.4 g)                                                                         (0.1 g)                                                                              8 hr  23.4%                                                                              decomposition                         9.   Anisole                                                                             t-butyl chloride                                                                         Mo(CO).sub.6                                                                         135°                                                                          9.5 g                                          (150 ml)                                                                            6.8 g)     0.03 g 24 hr 79%                                        10.  Phenol                                                                              t-butyl chloride                                                                         Mo(CO).sub.6                                                                         Reflux                                                                              18.8 g                                                                             120 ml heptane solvent,                          (12.0 g)   (0.01 g)                                                                             18 hr 96%  93% p-t-butylphenol, 3%                                                       2,6-di-t-butylphenol                  __________________________________________________________________________

                                      Table 2                                     __________________________________________________________________________    Acylation Reactions                                                           Aromatic   Organic  Added  Reaction                                           Substrate  Halide  Catalyst                                                                             Conditions                                                                          Yield  Comments                               __________________________________________________________________________    1. Toulene                                                                             Acetyl    Mo(CO).sub.6                                                                         Reflux                                                                              1.2 g                                                                              Only p-methyl aceto-                        (100 ml)                                                                            chloride (7.8 g)                                                                        (0.15 g)                                                                             24 hr 9%   phenone isolated                         2. Toulene                                                                             Propionyl Mo(CO).sub.6                                                                         Reflux                                                                              1.85 g                                                                             Only para acylation                         (160 ml)                                                                            chloride 6.35 g)                                                                        (0.05 g)                                                                             24 hr 18%  obtained                                 3. Toluene                                                                             Benzoyl chloride                                                                        Mo(CO).sub.6 Reflux                                                                             2.5 g Only p-methyl                         (160 ml)                                                                            6.05 g)   (0.15 g)                                                                             18 hr 29.7%                                                                              benzophenone isolated                    4. Toluene                                                                             Benzoyl chloride                                                                        TolMo(CO).sub.3                                                                      Reflux                                                                              5.65 g                                                                             Same product as 3                           (160 ml)                                                                            6.05 g)   (0.02 g)                                                                             12 hr 67%                                           5. Anisole                                                                             Acetyl chloride                                                                         Mo(CO).sub.6                                                                         100°                                                                         10.2 g                                                                             90% p-methoxyaceto-                         (125 ml)                                                                            7.8 g)    (0.02 g)                                                                             36 hr 68%  phenone, 4% o-methoxy-                                                        acetophenone                             6. Anisole                                                                             Benzoyl chloride                                                                        TolMo(CO).sub.3                                                                      100°                                                                         7.4 g                                                                              Only p-methoxybenzo-                        (150 ml)                                                                            (7.0 g    (0.15 g)                                                                             18 hr 70%  phenone isolated                         __________________________________________________________________________

                                      Table 3                                     __________________________________________________________________________    Polymerization Reactions                                                      Aromatic  Organic   Added                                                                               Reaction                                            Substrate Halide   Catalyst                                                                            Conditions                                                                           Yield  Comments                               __________________________________________________________________________    1. Durene                                                                              p-xylylene-                                                                             Mo(CO).sub.6                                                                         110°                                                                         9.6 g                                                                              Copolymer nearly insoluble                        dichloride                                                                              0.01 g 3 hr  (98%)                                                                              in common organic solvents               2. Benzyl          Mo(CO).sub.6                                                                         110°                                                                         100%                                             chloride        (0.1 g)                                                                              1 hr                                                   (neat)                                                                     3. Benzyl          TolMo(CO).sub.3                                                                      140°                                                                         100%                                             fluoride                                                                      (neat)                                                                     4. Diphenyl                                                                            Benzene-1,3-di-                                                                         Mo(CO).sub.6                                                                         110°                                                                         1.4 g                                                                              Tan-colored copolymer                       ether sulfonylchloride                                                                        (0.1 g)                                                                              3 hr  22%                                              (2.6 g                                                                              (4.3 g)                                                              5. Diphenyl                                                                            Benzene-1,3-di-                                                                         TolMo(CO).sub.3                                                                      110°                                                                         2.1 g                                                                              Same as 4                                   ether sulfonylchloride                                                                        (0.1 g)                                                                              3 hr  32%                                              (2.6 g)                                                                             (4.3 g)                                                              __________________________________________________________________________

                                      Table 4                                     __________________________________________________________________________    Sulfonylation Reactions                                                       Aromatic   Organic                                                                               Added                                                                              Reaction                                              Substrate  Halide Catalyst                                                                           Conditions                                                                           Yield  Comments                                 __________________________________________________________________________    1. Toluene                                                                             Tosyl chloride                                                                        Mo(CO).sub.6                                                                         Reflux                                                                              2.1 g                                                                              Product is 4,4'-                              (160 ml)                                                                            (3.8 g) (0.02 g)                                                                             36 hr 43%  ditolylsulfone                             2. Anisole                                                                             Tosyl chloride                                                                        Mo(CO).sub.6                                                                         135°                                                                         1.15 g                                                                             Product is 4-methyl-                          (160 ml)                                                                            (3.8 g) (0.02 g)                                                                             24 hr 22%  4'-methoxydiphenyl-                                                           sulfone                                    3. Anisole                                                                             Tosyl chloride                                                                        TolMo(CO).sub.3                                                                      115°                                                                         1.3 g                                                                              Same as 2                                     (160 ml)                                                                            (3.8 g) (0.03 g)                                                                             18 hr 25%                                             __________________________________________________________________________

                                      Table 5                                     __________________________________________________________________________    Dehydrohalogenation Reaction                                                  Aromatic Organic                                                                               Added Reaction                                               Substrate                                                                              Halide Catalyst                                                                             Conditions                                                                            Yield                                                                               Comments                                 __________________________________________________________________________    1. --  t-butyl chloride                                                                       Mo(CO).sub.6                                                                        reflux, 20 hr.                                                                         none                                                                              no reaction, 96% Mo(CO).sub.6                                                 recovered                                  2. --  t-butyl chloride                                                                       Toluene-                                                                            reflux, 4 hr.                                                                          --  large amounts of HCl evolved,                     (100 ml) Mo(CO).sub.3       2 polymeric substances                                     (200 mg)           obtained                                   __________________________________________________________________________

What is claimed is:
 1. The process of reacting an organic halide with an aromatic substrate to form an aromatic product comprising the steps of: charging a reaction vessel with a metallic hexacarbonyl compound having the general formula M(CO)₆ wherein M is selected from the group consisting of Cr, Mo and W, adding an aromatic substrate having the general formula ##SPC9##wherein R' is selected from the group consisting of hydrogen and sulfonyl chloride with the proviso that at least one of said R' is other than hydrogen, reacting said metallic hexacarbonyl compound with part of said aromatic substrate to yield an arene metal tricarbonyl catalyst having the general formula ##SPC10## charging the reaction vessel with an organic halide having the general formula RX wherein R is an alkyl group having from 1 to about 20 carbon atoms, and X is selected from the group consisting of bromine, chloride and fluorine, heating said reaction vessel from ambient temperatures to a temperature sufficient to cause said catalyst to remove the halide from said organic halide with generation of a carbonium ion from said organic halide so that said carbonium ion will attack the remaining part of said aromatic substrate to yield the aromatic product.
 2. The process as in claim 1, wherein said carbonium ion is formed in a temperature range from a few degrees above said ambient temperature to about 135°C.
 3. The process as in claim 1, wherein said reaction is carried out in an inert atmosphere.
 4. The process as in claim 3, wherein said inert atmosphere is nitrogen.
 5. The process as in claim 1, wherein said reaction is carried out in a solvent selected from the group consisting of a saturated liquid hydrocarbon and liquid aryl compounds.
 6. The process as in claim 1, wherein said organic alkyl halides are selected from the group consisting of n-propyl chloride, t-butyl chloride, cyclohexyl chloride, cyclohexyl fluoride, cyclohexyl bromide and n-chloroheptane.
 7. The process as in claim 1, wherein said aromatic substrate is benzene sulfonyl chloride.
 8. The process as in claim 1, wherein the metal of said arene metal tri-carbonyl catalyst is molybdenum. 